Be it known that I, Jeremy H. Klug, a citizen of United States, residing at Brunswick, Ohio, have invented a new and useful xe2x80x9cPROCESS TO REDUCE STICKING DURING SURFACE TREATMENT OF GRAPHITE ARTICLES.xe2x80x9d
The present invention relates generally to processes and systems for manufacturing articles from graphite material, and more particularly to processes for reducing sticking of the graphite material to a surface treatment tool such as an embossing tool during the manufacture of the articles. The articles may be formed into components of an electrochemical fuel cell.
An ion exchange membrane fuel cell, more specifically a proton exchange membrane (PEM) fuel cell, produces electricity through the chemical reaction of hydrogen and oxygen in the air. Within the fuel cell, electrodes denoted as anode and cathode surround a polymer electrolyte to form what is generally referred to as a membrane electrode assembly, or MEA. Oftentimes, the electrodes also function as the gas diffusion layer (or GDL) of the fuel cell. A catalyst material stimulates hydrogen molecules to split into hydrogen atoms and then, at the membrane, the atoms each split into a proton and an electron. The electrons are utilized as electrical energy. The protons migrate through the electrolyte and combine with oxygen and electrons to form water.
A PEM fuel cell is advantageously formed of a membrane electrode assembly sandwiched between two graphite flow field plates. Conventionally, the membrane electrode assembly consists of random-oriented carbon fiber paper electrodes (anode and cathode) with a thin layer of a catalyst material, particularly platinum or a platinum group metal coated on isotropic carbon particles, such as lamp black, bonded to either side of a proton exchange membrane disposed between the electrodes. In operation, hydrogen flows through channels in one of the flow field plates to the anode, where the catalyst promotes its separation into hydrogen atoms and thereafter into protons that pass through the membrane and electrons that flow through an external load. Air flows through the channels in the other flow field plate to the cathode, where the oxygen in the air is separated into oxygen atoms, which joins with the protons through the proton exchange membrane and the electrons through the circuit, and combine to form water. Since the membrane is an insulator, the electrons travel through an external circuit in which the electricity is utilized, and join with protons at the cathode. An air stream on the cathode side is one mechanism by which the water formed by combination of the hydrogen and oxygen is removed. Combinations of such fuel cells are used in a fuel cell stack to provide the desired voltage.
One limiting factor to the use of graphite materials, especially flexible graphite materials, as components for PEM fuel cells is the definition of a pattern embossed on the material, which, if not sufficient, can interfere with operation of the fuel cell, by either permitting leaking of fluids, or not permitting sufficient fluid flow through the fuel cell.
Graphites are made up of layer planes of hexagonal arrays or networks of carbon atoms. These layer planes of hexagonally arranged carbon atoms are substantially flat and are oriented or ordered so as to be substantially parallel and equidistant to one another. The substantially flat, parallel equidistant sheets or layers of carbon atoms, usually referred to as graphene layers or basal planes, are linked or bonded together and groups thereof are arranged in crystallites. Highly ordered graphites consist of crystallites of considerable size: the crystallites being highly aligned or oriented with respect to each other and having well ordered carbon layers. In other words, highly ordered graphites have a high degree of preferred crystallite orientation. It should be noted that graphites by definition possess anisotropic structures and thus exhibit or possess many properties that are highly directional e.g. thermal and electrical conductivity and fluid diffusion.
Briefly, graphites may be characterized as laminated structures of carbon, that is, structures consisting of superposed layers or laminae of carbon atoms joined together by weak van der Waals forces. In considering the graphite structure, two axes or directions are usually noted, to wit, the xe2x80x9ccxe2x80x9d axis or direction and the xe2x80x9caxe2x80x9d axes or directions. For simplicity, the xe2x80x9ccxe2x80x9d axis or direction may be considered as the direction perpendicular to the carbon layers. The xe2x80x9caxe2x80x9d axes or directions may be considered as the directions parallel to the carbon layers or the directions perpendicular to the xe2x80x9ccxe2x80x9d direction. The graphites suitable for manufacturing flexible graphite sheets possess a very high degree of orientation.
As noted above, the bonding forces holding the parallel layers of carbon atoms together are only weak van der Waals forces. Natural graphites can be chemically treated so that the spacing between the superposed carbon layers or laminae can be appreciably opened up so as to provide a marked expansion in the direction perpendicular to the layers, that is, in the xe2x80x9ccxe2x80x9d direction, and thus form an expanded or intumesced graphite structure in which the laminar character of the carbon layers is substantially retained.
Graphite flake which has been chemically or thermally expanded and more particularly expanded so as to have a final thickness or xe2x80x9ccxe2x80x9d direction dimension which is as much as about 80 or more times the original xe2x80x9ccxe2x80x9d direction dimension can be formed without the use of a binder into cohesive or integrated sheets of expanded graphite, e.g. webs, papers, strips, tapes, or the like (typically referred to as xe2x80x9cflexible graphitexe2x80x9d). The formation of graphite particles which have been expanded to have a final thickness or xe2x80x9ccxe2x80x9d dimension which is as much as about 80 times or more the original xe2x80x9ccxe2x80x9d direction dimension into integrated flexible sheets by compression, without the use of any binding material, is believed to be possible due to the mechanical interlocking, or cohesion, which is achieved between the voluminously expanded graphite particles.
In addition to flexibility, the sheet material, as noted above, has also been found to possess a high degree of anisotropy with respect to thermal and electrical conductivity and fluid diffusion, comparable to the natural graphite starting material due to orientation of the expanded graphite particles substantially parallel to the opposed faces of the sheet resulting from very high compression, e.g. roll pressing. Sheet material thus produced has excellent flexibility, good strength and a very high degree of orientation.
Briefly, the process of producing flexible, binderless anisotropic graphite sheet material, e.g. web, paper, strip, tape, foil, mat, or the like, comprises compressing or compacting under a predetermined load and in the absence of a binder, expanded graphite particles which have a xe2x80x9ccxe2x80x9d direction dimension which is as much as about 80 or more times that of the original particles so as to form a substantially flat, flexible, integrated graphite sheet. The expanded graphite particles that generally are worm-like or vermiform in appearance, once compressed, will maintain the compression set and alignment with the opposed major surfaces of the sheet. The density and thickness of the sheet material can be varied by controlling the degree of compression. The density of the sheet material is typically within the range of from about 0.04 g/cc to about 1.4 g/cc. The flexible graphite sheet material exhibits an appreciable degree of anisotropy due to the alignment of graphite particles parallel to the major opposed, parallel surfaces of the sheet, with the degree of anisotropy increasing upon roll pressing of the sheet material to increased density. In roll pressed anisotropic sheet material, the thickness, i.e. the direction perpendicular to the opposed, parallel sheet surfaces comprises the xe2x80x9ccxe2x80x9d direction and the directions ranging along the length and width, i.e. along or parallel to the opposed, major surfaces comprises the xe2x80x9caxe2x80x9d directions and the thermal, electrical and fluid diffusion properties of the sheet are very different, by orders of magnitude typically, for the xe2x80x9ccxe2x80x9d and xe2x80x9caxe2x80x9d directions.
This considerable difference in properties, i.e. anisotropy, which is directionally dependent, can be disadvantageous in some applications. For example, in gasket applications where flexible graphite sheet is used as the gasket material and in use is held tightly between metal surfaces, the diffusion of fluid, e.g. gases or liquids, occurs more readily parallel to and between the major surfaces of the flexible graphite sheet. It would, in most instances, provide for greater gasket performance, if the resistance to fluid flow parallel to the major surfaces of the graphite sheet (xe2x80x9caxe2x80x9d direction) were increased, even at the expense of reduced resistance to fluid diffusion flow transverse to the major faces of the graphite sheet (xe2x80x9ccxe2x80x9d direction). With respect to electrical properties, the resistivity of anisotropic flexible graphite sheet is high in the direction transverse to the major surfaces (xe2x80x9ccxe2x80x9d direction) of the flexible graphite sheet, and substantially less in the direction parallel to the major faces of the flexible graphite sheet (xe2x80x9caxe2x80x9d direction). In applications such as electrodes for fuel cells, it would be of advantage if the electrical resistance transverse to the major surfaces of the flexible graphite sheet (xe2x80x9ccxe2x80x9d direction) were decreased, even at the expense of an increase in electrical resistivity in the direction parallel to the major faces of the flexible graphite sheet (xe2x80x9caxe2x80x9d direction).
With respect to thermal properties, the thermal conductivity of a flexible graphite sheet in a direction parallel to the major surfaces of the flexible graphite sheet is relatively high, while it is relatively low in the xe2x80x9ccxe2x80x9d direction transverse to the major surfaces.
Flexible graphite sheet can also be provided with channels, which are preferably smooth-sided, and which pass between the parallel, opposed surfaces of the flexible graphite sheet and are separated by walls of compressed expanded graphite. When such a flexible graphite sheet functions as an electrode in an electrochemical fuel cell, it is placed so as to abut the ion exchange membrane, so that the xe2x80x9ctopsxe2x80x9d of the walls of the flexible graphite sheet abut the ion exchange membrane.
There is a continuing need for improved processes for the manufacture of graphite articles by various forming techniques such as rotary embossing, platen press embossing and perforating, and there is a need for the prevention of the sticking of the graphite materials and particularly the resin of resin impregnated graphite materials to the forming tools. The present invention provides such improved processes, which are particularly useful in the manufacture of materials which can be formed into components of electrochemical fuel cells.
The present invention provides a method of manufacturing articles from graphite material, the method including steps of:
(a) providing a temporary non-stick coating between a surface of the graphite material and a forming tool;
(b) engaging the surface of the article with the forming tool, with the non-stick coating therebetween, and applying pressure to the surface with the forming tool and thereby forming the article; and
(c) removing the forming tool from the surface; wherein the non-stick coating disposed between the surface of the graphite material and the forming tool reduces adherence of the article to the forming tool.
In one embodiment, the temporary non-stick coating takes the form of a sprayed aerosol polymer material such as a liquid based silicone sprayed intermittently upon the forming tool. Thus, an aerosol sprayed-on layer of non-stick material is temporarily provided between the forming tool and the surface of the graphite material which is engaged by the forming tool. Preferably, a plurality of articles will be formed between the intermittent sprayings of the forming tool. An aerosol may also be used to carry a layer of solid particles, such as polytetrafluroethylene, e.g. Teflon, to coat the forming tool.
In another embodiment, the non-stick material takes the form of a flexible sheet of solid non-stick material, such as polyethylene or other polymeric material. The flexible sheet of non-stick material is sandwiched between the forming tool and the surface of the graphite material, which is engaged by the forming tool. After the article is formed, the sheet of non-stick material may be peeled away from the article.
Preferably, the forming tool takes the form of at least one of the pair of embossing rollers, and the graphite material is in the form of a sheet of graphite material being pulled through the embossing rollers. The forming tool can comprise both of the rollers, and both rollers can include forming features.
When using the sheet of solid non-stick material, it may be provided on a supply roll provided upstream of the embossing rollers, and may be retrieved with a takeoff roll downstream of the embossing rollers.
In another embodiment, the supply roll of non-stick material may be located upstream of a calendering roller so as to provide the double duty of preventing sticking of the graphite material to both one or more of the calendering rollers and the embossing roller.
Thus, an object of the present invention is the provision of methods of manufacturing graphite articles with a forming tool, and preventing sticking of the graphite material to the forming tool.
Another object of the present invention is the provision of methods for handling flexible sheets of resin impregnated graphite material during a forming process.
And another object of the present invention is the prevention of sticking of graphite material to a forming tool.
And another object of the present invention is the provision of methods for preventing adherence of resin from a resin impregnated graphite material on either a calendering roller or an embossing roller used to manufacture the sheets of graphite material and to form articles therefrom.
And another object of the present invention is the provision of economical methods of manufacturing articles from flexible sheets of graphite material.
Still another object is the provision of methods of manufacturing components of fuel cells from graphite materials.